This invention relates to a process for removing HCl and HF from coal derived fuel gas at elevated temperatures by contacting the gas with sorbents such as nahcolite, sodium bicarbonate or sodium carbonate in a powder form.
In coal gasification processes, the coal derived fuel gas contains HCl and HF at a combined concentration of about 50-1000 ppm. These gas species are acidic in a wet environment and it is desirable that they be removed to prevent corrosion of downstream equipment and to minimize acid gas emissions to the environment.
At the same time, it is well known that gases derived from coal gasification techniques also contain sulphur compounds which must be removed in order to meet environmental standards and to prevent damage to equipment. These sulphur compounds generally include primarily hydrogen sulphide (H.sub.2 S) and, in lesser amounts, carbonyl sulphide (COS) and the like. A great deal of attention has been focused on sulfur compound removal from gases. For example, see U.S. Pat. Nos. 1,816,533; 2,259,409; 2,682,444; 2,983,573; 4,088,736; 4,089,809; 4,251,495; 4,273,749; 4,310,497; 4,435,371; 4,442,078; 4,478,800; and 4,489,047.
A process for removing sulphur species and particulates from coal derived fuel gases was disclosed in commonly owned U.S. Pat. No. 4,857,285, the entirety of which is expressly incorporated herein by reference.
Briefly, in the '285 patent, a process is described for removing gaseous sulfur compounds from a hot gas by (a) contacting the hot gas with at least one metal oxide sorbent in a bed of metal oxide sorbent which is movable in a direction countercurrently to the hot gas, whereby the metal oxide sorbent reacts with the hydrogen sulfide and other sulfide compounds to form a spent or sulfur-rich metal sorbent and a hot gas lean in or depleted of sulfur compounds; (b) removing the hot gas lean in sulfur from the bed of metal oxide sorbent; (c) contacting the sulfur-rich metal sorbent with a first oxygen-containing gas which moves cocurrently in the direction of a movable bed of the sulfur-rich metal absorber in a first phase regeneration to convert, in an exothermic reaction, sulfur-rich metal sorbent to a partially-sulfided sorbent (partially spent metal-sulfur compound), thereby forming a sulfur dioxide-containing gas; (d) contacting the partially-sulfided sorbent with a second oxygen-containing gas which moves co-currently in the direction of a movable bed of the partially-sulfided sorbent in a second phase regeneration to convert, in an exothermic reaction, the partially-sulfided sorbent to regenerated or re-usable metal oxide and thereby forming additional sulfur dioxide-containing gas, the first oxygen-containing gas having a concentration of oxygen which is less than the concentration of oxygen in the second oxygen-containing gas; (e) contacting the regenerated metal oxide with air, oxygen-enriched air or oxygen which moves countercurrently to the direction of a movable bed of the regenerated metal oxide to ensure completion of regeneration, to cool the regenerated metal oxide and to purge the regenerated metal oxide of sulfur dioxide-containing gas; (f) removing the sulfur dioxide-containing gas purged from the regenerated metal oxide; and (g) reusing the regenerated metal oxide in step (a). In an optional step, the patent indicates that a slip stream of the hot gas lean in sulfur compounds may be passed through regenerated metal oxide whereby residual metal sulfate compounds in the regenerated metal oxide are decomposed, and oxidized regenerated metal oxide is chemically reduced.
It would be advantageous of course to be able to remove HCl and HF concurrently with the removal of the sulfur compounds, but no such process has heretofore been available. This invention relates to a process for removing HC1 and HF compounds which can be coupled with the desulfurization process as described in the '285 patent.
By way of background, it has been experimentally confirmed in the laboratory that HCl can be removed from coal gas via contact with a sorbent such as nahcolite. The known chemical reaction between HCl and nahcolite is as follows: EQU NaHCO.sub.3 +HCl.fwdarw.NaCl+CO.sub.2 +H.sub.2 O (1)
Similarly, the chemical reaction between HF and nahcolite is as follows: EQU NaHCO.sub.3 +HF.fwdarw.NaF+CO.sub.2 +H.sub.2 O (2)
The products of both reactions are gaseous CO.sub.2 and H.sub.2 O, and solid salts, i.e., NaCl in the case of reaction (1) and NaF in the case of reaction (2).
Krishnan et al. in a publication entitled: "High Temperature Coal Gas Chloride Clean-up for Molten Carbonate Fuel Cell Applications, Final Report" (G. N. Krishnen, G. T. Tong, B. J. Wood and N. Korens, Nov. 1986) reported laboratory experiments in which coal gas chloride removal was performed at 527.degree. to 650.degree. C. It was found that HCl can be removed effectively from a concentration of 300 ppm to a concentration of 1-5 ppm in a fixed bed with a rather short residence time. Their proposed commercial scale HCl removal concept consists of two fixed bed vessels containing pelletized nahcolite. One vessel absorbs HCl and HF, the other is maintained on a standby basis, or is used for loading/unloading sorbent/reaction product respectively.
The present invention relates to coupling a simple and cost effective process for removing the HCl and HF with the existing sulphur compound removal process as disclosed in the above identified '285 patent in the treatment of coal derived fuel gas. As a result, a system is provided which is capable of removing all of the major pollutants from the coal derived fuel gas.
With reference now to FIG. 1, a system for removing sulphur species and particulates from coal derived fuel gases at elevated temperature and pressure is shown generally at 10. A stream 12 of coal derived fuel gas containing particulate matter, sulphur species including H.sub.2 S, COS and CS.sub.2, as well as HCl and HF, at a temperature of between 350.degree.-700.degree. C. and a pressure of up to 600 p.s.i.g. flows into a primary cyclone 14 which removes entrained particulates via stream 16. The gas effluent from the primary cyclone 14 flows away from the primary cyclone via stream 18 and is injected into an absorber 20. The absorber 20 comprises a countercurrent moving bed reactor containing a metal oxide in granular form. The metal oxide is an absorbent which reacts with the sulphur species to form metal sulphide. The absorber also comprises a granular bed filter which further removes entrained particles from the gas stream 18. The particulates captured by the absorber 20 move with the bed material in a stream 22 into a regenerator 24. A stream 26 carries the particulates from the regenerator 24 to a fines separator 28 located below the regenerator. The fine particulates separated within the separator 28 are carried away from the separator in stream 30, while coarse material from the fines separator 28 is led via stream 32 to a sorbent elevator 34 which recycles the coarse material via a stream 36 back to the top of the absorber 20.
The primary stream 38 of cleaned gas from the absorber 20 is directed to a secondary cyclone 40 for additional particulate removal. It will be understood by those of ordinary skill in the art that stringent emission requirements may require the replacement of the secondary cyclone with a conventional barrier filter or the like. Particulates are carried away from the secondary cyclone or barrier filter 40 via stream 42, while cleaned gas exits the secondary cyclone or alternate particulate removal system via stream 44, and is fed to a power plant which may comprise a gas turbine generator 45.
In accordance with this invention, a process for removing HCl and HF from coal derived fuel gas in combination with the removal of sulphur species and particulates as described above is provided.
Specifically, the removal of HCl and HF is achieved by contacting nahcolite ( a naturally occurring form of sodium bicarbonate), sodium bicarbonate, sodium carbonate or Trona (a naturally occurring mixture of sodium bicarbonate and sodium carbonate) in a powder form with the coal derived fuel gas stream at elevated temperatures. With specific reference to the sulphur removal system described above, and as disclosed in the '285 patent, four alternate locations have been identified for the introduction of the sorbent material as described in greater detail further herein.
In its broader aspects, therefore, the present invention relates to an improved process for removing HCl and HF in a known process for removing sulfur compounds from a hot gas stream containing H.sub.2 S, COS, HCl and HF comprising:
(a) introducing a sorbent material at a location and in an amount effective to break down at least the HCl and HF constituents into solid salts and gaseous CO.sub.2 and H.sub.2 O; and PA1 (b) removing the solid salts from the stream. PA1 (a) passing the stream into a primary cyclone; PA1 (b) passing gas effluent from the primary cyclone into an absorber containing a sulfur sorbent; PA1 (c) passing a primary stream of cleaned gas from the absorber into a secondary cyclone or alternate particulate removal system for additional removal of particulate material from the primary stream; and PA1 (d) introducing an HCl/HF sorbent into the process stream in an amount and at a location effective to react with HCl/HF in the gas stream to produce solid NaCl and NaF, gaseous CO.sub.2 and H.sub.2 O. PA1 (a) passing the stream into a primary cyclone; PA1 (b) passing gas effluent from the primary cyclone into an absorber containing a sulfur sorbent; PA1 (c) passing a primary stream of cleaned gas from the absorber into a secondary cyclone or alternate particulate removal system for additional removal of particulate material from the primary stream; PA1 (d) simultaneously with step (c), passing particulates captured in the absorber to a regenerator; PA1 (e) passing particulates from the regenerator to a fines separator; PA1 (f) passing coarse material from the fines separator to a sorbent elevator; PA1 (g) recycling coarse material from the sorbent elevator to the absorber; and PA1 (h) introducing an HCl/HF sorbent into the process stream in an amount and at a location effective to react with HCl and/or HF in the gas stream to produce solid NaCl and/or NaF, gaseous CO.sub.2 and H.sub.2 O.
In another aspect, the invention relates to a process for removing pollutants from a hot sulphur and hydrogen chloride and/or hydrogen fluoride laden gas stream comprising the steps of:
In still another aspect, the invention relates to a process of removing pollutants from a hot sulfur and hydrogen chloride and/or hydrogen fluoride laden gas stream comprising the steps of:
Additional objects and advantages of the invention disclosed herein will be apparent from the detailed description which follows.